Dinitrogen-supported coordination polymers

Abstract

The one-pot solvothermal reactions of 3- and 4-(aminomethyl)pyridine with triethyl orthoformate and Cu(O₂CCH₃)₂ in methanol saturated with dinitrogen afforded the first examples of coordination polymers that are supported by dinitrogen, namely [Cu_2.5(3-mpyf)(N₂)_1.5]_n [3-Hmpyf = N,N′-bis(pyridine-3-ylmethyl)formamidine], 1, and {[Cu₃(4-Hmpyf)(N₂)₃]·(CH₃OH)}_n [4-Hmpyf = N,N′-bis(pyridine-4-ylmethyl)formamidine], 2. The dinitrogen anions of 1 adopt the end-on-dinuclear (μ-η¹:η¹) bonding mode, resulting in a 4,4-connected binodal net with the new (5³·7³)₂(5⁴·8²) topology, and those of 2 display both end-on-dinuclear and end-on-trinuclear (μ-η¹:η¹:η¹) bonding modes, forming a 3,8-connected binodal net with the rare (5³)₄(5⁸·6⁴·7⁸·8⁴·9⁴)₂-3,8T16 topology.